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Design of cavities for a target molecule and the elucidation of the corresponding host–guest interactions are important for molecular manipulation. A discrete dodecavanadate bowl, [V12O32]4− (V12), with an entrance diameter of 4.4 Å and an electron‐rich guest at the center of the bowl, was stabilized by electrostatic interactions. A characteristic of V12 is a solid‐state polytopal rearrangement during...
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